CN102906123A - Nanocomposite biomaterials of nanocrystalline cellulose (ncc) and polylactic acid (pla) - Google Patents

Nanocomposite biomaterials of nanocrystalline cellulose (ncc) and polylactic acid (pla) Download PDF

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CN102906123A
CN102906123A CN2011800092629A CN201180009262A CN102906123A CN 102906123 A CN102906123 A CN 102906123A CN 2011800092629 A CN2011800092629 A CN 2011800092629A CN 201180009262 A CN201180009262 A CN 201180009262A CN 102906123 A CN102906123 A CN 102906123A
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W·Y·哈马德
苗传威
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    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
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Abstract

A new approach is conceived for the development of sustainable biomaterials comprising nanocrystalline cellulose (NCC) and polylactic acid (PLA) nanocomposites. The invention deals with advancing a method based on in situ ring opening polymerization of L-lactide in the presence of NCC particles to form NCC-PLA supramolecular nanocomposite materials. This material is hydrophobic and compatible with a wide range of synthetic and natural polymers. NCC-PLA nanocomposites have enhanced functionality (e.g. gas barrier), rheological and mechanical performance, as well as dimensional stability (i.e. less hygroexpansivity) relative to PLA. They are made from entirely renewable resources, and are potentially biocompatible as well as recyclable. NCC-PLA supramolecular nanocomposites can be suspended in most organic solvents or dried to form a solid substance. They can be processed using conventional polymer processing techniques to develop 3-dimensional structures, or spun into fibres, yarns or filaments.

Description

The nano combined biomaterial of nanocrystalline Mierocrystalline cellulose (NCC) and poly(lactic acid) (PLA)
Technical field
The present invention relates to the nano-complex of a kind of nanocrystalline Mierocrystalline cellulose (NCC) and poly(lactic acid) (PLA), and the method for preparing this nano-complex.This nano-complex is lasting, heat-staple biomaterial, and it is hydrophobic and with a large amount of synthetic compatible with natural polymer.The NCC-PLA nano-complex has the mechanical property of enhancing and dimensional stability (namely still less hygroexpansivity) with respect to PLA, and has potential biocompatibility, recyclability and by complete renewable resources preparation again.The NCC-PLA nano-complex can be suspended in many organic solvents or the dry solid matter that forms, and it can process to develop three-dimensional structure with the conventional polymer processing technology.
Background technology
In all many-sides, 20th century showed as plastics century.Can not imagine our times and not have plastics.Product scope from the baby bottle to wrapping material to aircraft component.Although polyolefine has been the basis of nearly all commercial plastics exploitation, but owing to relating to recirculation, health and Environmental liability, problem about their prolonged application also highlights, for instance, in making polycarbonate plastic and Resins, epoxy, need to use the chemical fundamentals component, such as dihydroxyphenyl propane (BPA).
As response, development by the work of the biological plastics of renewable resources preparation and biomaterial in making great efforts to carry out.Nanocrystalline Mierocrystalline cellulose (NCC) is high crystalline cellulose, extracts from wooden or non-Wooden Biomass.Poly(lactic acid) (PLA) is thermoplastic aliphatic polyester, is comprised of lactic acid (2-ethylene-lactic acid) basic component.PLA stems from renewable plant resources, for example starch and sugar, and have potential application aspect medicine, engineering and food and the drink pack.The degraded of PLA can be finished by the hydrolysis of ester bond, and does not need enzyme to process.Yet PLA compares with polyolefine has certain limitation, and particularly in the course of processing, this has greatly limited its application.PLA is essentially hygroscopic and has low heat resistant.Nanoscale strengthens rheological property, mechanical property and the physicals that can be used for improving polymkeric substance, improves thus their processibility, functional and final use properties.Because its huge specific surface area, high strength and high surface, NCC can be used as high-performance reinforcing agent.In order to reach this purpose, need two key conditions: (i) the fabulous dispersion of NCC in polymeric matrix, and (ii) in order to prepare interface structure fabulous in the varying environment, between the two perfect consistency.
Studies show that at the above NCC of substrate glass transition temperature and can be used for the storage modulus of some nano-complexes is improved several orders of magnitude [1-3].By compounding NCC and PLA, might produce biomaterial, it is prepared by complete renewable resources, has gratifying performance.Yet because NCC is hydrophilic and PLA is hydrophobicity, consistency becomes key and hard problem.The result who has announced shows, by direct compounding PLA and unmodified or only to prepare the NCC-PLA nano-complex with the NCC of tensio-active agent or Its Compatibilizing Technology physically modified almost be impossible [4-8].Nearer studies show that, the dispersion of NCC in the PLA matrix can be by improving [9] with polycaprolactone (PCL) graft N CC.Yet, in such system, still observe the gathering of nanoparticle, and the raising of the mechanical property of the nano-complex that obtains is limited.
Summary of the invention
The present invention seeks to provide the nano-complex of a kind of nanocrystalline Mierocrystalline cellulose (NCC) and poly(lactic acid) (PLA).
The present invention also seeks to provide a kind of method for preparing the nano-complex of nanocrystalline Mierocrystalline cellulose (NCC) and poly(lactic acid) (PLA).
The present invention also further seeks to provide a kind of composition that comprises nano-complex of the present invention, itself and high molecular PLA compounding or blend.
In one aspect of the invention, provide the nano-complex of a kind of nanocrystalline Mierocrystalline cellulose (NCC) and poly(lactic acid) (PLA), wherein said PLA is grafted on the described NCC.
In another aspect of the present invention, a kind of method for preparing the nano-complex of nanocrystalline Mierocrystalline cellulose (NCC) and poly(lactic acid) (PLA) is provided, the method is included in the ring-opening polymerization of L-rac-Lactide in the presence of the NCC particle in the non-aqueous media.
Of the present invention aspect another, provide a kind of composition that comprises nano-complex of the present invention, itself and the polymkeric substance (for example high molecular PLA) compounding or the blend that are selected from PLA, poly butyric ester (PHB) or polyhydroxyalkanoate (PHA).
Above-mentioned compounding or blend can be undertaken by for example coextrusion, injection moulding or other polymer processing technology.
Description of drawings
Fig. 1: be the flow chart of steps of L-rac-Lactide and the copolymerization of NCC situ-formed graft.
Fig. 2: solid-state for NCC, PLA and NCC-PLA nano-complex 13C nucleus magnetic resonance (NMR) spectrogram.The independent peak of nanocomposite samples peak and NCC and PLA is complementary, and the synthetic of success carried out in this original position ring-opening polymerization that shows use L-rac-Lactide in the presence of NCC.
Fig. 3: be the means of differential scanning calorimetry response curve of PLA and NCC-PLA nano-complex film.The nano-complex film is with respect to the apparent crystallization that goes out remarkable improvement of PLA, and this shows structural integrity, heat and the dimensional stability of raising.In fact, NCC can help to overcome the problem of PLA processing and conversion.(T g=second-order transition temperature; T c=Tc; T m=melt temperature)
Fig. 4: be temperature variant storage modulus curve, it shows that the PLA casting film is than the dynamic mechanical response of the compatibilized NCC casting film with Different Weight ratio.The NCC content that increases has shown the property of softening that the finished product improve, and it shows higher degree of crystallinity.Compatibilized NCC or NCC-PLA supramolecular materials prepared in accordance with the present invention are by casting film and technical grade PLA blend.
Fig. 5: be temperature variant storage modulus curve, it shows PLA and by being different from the dynamic mechanical response of the NCC-PLA nano composite membrane that method shown in Figure 4 makes.These samples are compound by coextrusion, and then compression molding is to form film.Frigorimeter understands this process fast, and PLA is unbodied fully.The NCC content that increases shows the ability of the degree of crystallinity that improves the finished product, and the ability that therefore improves the mechanical response of the finished product.
Embodiment
The present invention relates to a kind ofly be used to developing novel method durable, heat-staple biomaterial, this biomaterial comprises nanocrystalline Mierocrystalline cellulose (NCC) and poly(lactic acid) (PLA) nano-complex.This novel method utilizes the original position ring-opening polymerization of NCC particle and L-rac-Lactide to form the NCC-PLA nano composite material.The material that obtains is hydrophobic and with a large amount of synthetic or natural polymer is compatible.The NCC-PLA nano-complex has the mechanical property of enhancing and dimensional stability (namely still less hygroexpansivity) with respect to PLA.They have potential biocompatibility, can reclaim and be made by complete renewable resources.They can be suspended in the majority of organic solvent or the dry solids that forms, and it can utilize the traditional polymer processing technology to process to produce three-dimensional structure.
Nanocrystalline Mierocrystalline cellulose (NCC) is colloidal suspended substance by the acid hydrolysis extraction of typical chemical wood pulp, but other cellulose materials also can use such as marine animal (for example tunicate) or the cotton of bacterium, cellulose.NCC is made of Mierocrystalline cellulose, and this Mierocrystalline cellulose is that its chain alignment forms crystal and amorphous domain by the linear polymer of the D-Glucose unit of β (1 → 4) connection.
Extract the polymerization degree (DP) and per 100 the anhydroglucose unit 3.7-6.7 sulfate groups that the NCC that obtains has 90≤DP≤110 by hydrolysis.NCC comprises crystallite, and according to raw materials used in extracting, its physical size scope is 5-10nm at cross section, is 20-100nm in length.If suitably derivative or form solid material by air, spraying or lyophilize self-assembly, these charged crystallites can be suspended in the water or in other solvent.When drying, NCC forms the coacervate of bar-shaped parallelepiped structure, and it has the cross section (5-20nm) of nanometer range, and their length is the larger order of magnitude (100-1000nm) simultaneously, and this has caused high aspect ratio.The characteristics of NCC also are high-crystallinity (＞80%, more likely between 85% and 97%), and this is close to the theoretical limit of cellulose chain.Hydrogen bond between the cellulose chain can be stablized the local structure of NCC, and plays a key effect in the formation of crystalline region.Degree of crystallinity is defined as the crystalline fraction of sample, greatly affects the physics and chemistry performance of NCC.For example, the degree of crystallinity of NCC directly affects chemically derived feasibility, swelling and water viscosity.
Do not exist the PLA of lower L-rac-Lactide ring-opening polymerization formation to compare with there being NCC, nano-complex of the present invention is hydrophobic and molded feature, thermomechanical property and gas barrier property that have raising.
In this process, so that the in-situ polymerization that the PLA grafting is formed on the NCC is caused by the hydroxyl on the NCC, perhaps can partly cause and partly provide by the initiator that adds the source of hydroxyl groups of polyreaction by the hydroxyl on the NCC, for example pure, the suitable alcohol that is used for polymerization system comprises phenylcarbinol and DODECANOL, 1-.
NCC in the nano-complex has kept the crystallization property of the front original NC C of grafting.Yet, when with (i.e. grafting PLA on the NCC) compounding of NCC-PLA nano composite material or blend, the crystallization property of PLA is by the NCC modification, and the PLA nano-complex reaches than there not being the higher degree of crystallinity of PLA (being parent PLA) that the ring-opening polymerization of L-rac-Lactide forms in the presence of the NCC.The crystalline state of the material of the PLA of grafting and subsequently compounding or blend is more stable than the crystalline state of parent PLA.
Open ring lactone has terminal carboxyl(group) and hydroxyl; In the formation of polymer chain, the carboxylic acid of the hydroxyl of an open loop unit and another open loop unit forms ester and is connected, and form chemistry with NCC between the hydroxyl of the end carboxyl of polymer chain and NCC and be connected or key, thus the formation ester bond.Therefore, between each independent polymer chain and NCC, form singly-bound.In other words, the end of the PLA chain of grafting is bonded on the NCC by the monoester bond that forms in polymerization process.In principle, the hydroxyl on the NCC can be taken on the initiator of rac-Lactide polymerization.
Nano-complex will have several perhaps many polymer chains that are linked to independently on each NCC nanocrystal; Be the structure that each NCC crystal comprises formation central crystal, several polymkeric substance or a plurality of chain are sent by it.NCC by this mode modification becomes in chloroform and can disperse, and it is the good solvent of PLA.
Molecular weight and the conversion of monomer degree of the free PLA homopolymer that produces in the home position polymerization reaction process depend on reaction conditions, particularly the concentration of NCC in the consumption of monomer and the reaction medium.Usually, be defined as that grafting and free PLA total mass account for the conversion of monomer degree of ratio of used L-rac-Lactide quality and the molecular weight of the NCC-PLA nano composite material that obtains all non-linearly improves along with the raising of monomer consumption and NCC concentration.
For example, if monomer maintains constant at 30: 1 with respect to the quality ratio of NCC, the quality that is the L-lactide monomer is 30 times of NCC quality, but the concentration of NCC in solvent (for example DMSO) is increased to 2.5g/100ml from 1.5g/100ml, and other all conditions is when keeping identical, and number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of conversion of monomer degree, NCC-PLA nano composite material will be increased to 44.8%, 5532 and 19803 from 12.7%, 1561 and 1989 respectively.
Ring-opening polymerization is more particularly carried out under anhydrous condition.In the anhydrous response medium concentration of NCC can be typically from 1 to 10g/100mL, preferably from 1.5 to 5g/100mL, and the quality 5-50 of L-rac-Lactide is doubly to the quality of initial NCC, preferred 15-30 doubly.
After thoroughly free homopolymer and unreacted chemical medicine are removed in cleaning, nano-complex will typically have usually from 30% to the PLA percentage of grafting that surpasses 90%, but more generally approximately 85%, the PLA percentage of grafting is defined as the quality of PLA of grafting and the ratio of NCC quality.In other words, the quality of PLA will be the quality of initial NCC * 85% in the nano-complex that obtains.
Particularly, polyreaction is for example carried out in the dimethyl sulfoxide (DMSO) (DMSO) at organic solvent.In addition, the medium that is used for home position polymerization reaction can be but be not limited to alcohols (such as methyl alcohol), amides (such as dimethyl formamide), amine (such as pyridine), ester class (such as ethyl acetate), ethers (such as 1, the 4-dioxane), dibasic alcohol ethers (such as butoxy ethanol), halogenation kind solvent (such as chloroform), varsol (such as toluene) and ketone (such as acetone).
NCC exists the in-situ polymerization of lower L-rac-Lactide to cause forming the PLA of various chain lengths.This PLA is partially grafted to NCC, namely as mentioned shown in, be generally 30-90%, typically be 85%.Remaining is free PLA homopolymer and unreacted monomer.Purification etc. can be removed any unreacted PLA monomer and free PLA homopolymer.
Therefore, after the polyreaction be the step that from anhydrous medium, reclaims nano-complex.Particularly, this recycling step can comprise precipitate nano-complex from anhydrous medium, and the precipitation that obtains by dialysis and/or centrifugal purification.The quality of the free PLA homopolymer that obtains in reaction process typically is 2-15 doubly to the quality of initial NCC.This greatly depends on polymeric reaction condition.Yet, have been found that keeping some free PLA homopolymer promotes the good distribution of nano-complex and guarantee that good interface (being good consistency) is favourable for auxiliary in the subsequent technique of nano-complex.Present stage, how many free PLA homopolymer we need can not quantize.The free homopolymer of preparation finds to be conducive to guarantee (i) mixture Uniform Dispersion in processed products arbitrarily thus, and (ii) and in polymer processing afterwards the good interface of used resin, typically, but be not necessarily limited to PLA.
Ring-opening polymerization is carried out under the temperature that improves, and typically is approximately 100 ℃-Yue 150 ℃, and more particularly approximately 130 ℃, and be generally 1-20 hour time, more particularly approximately 15-20 hour.
Suitably, ring-opening polymerization is carried out in the presence of catalyzer, typically is metal carboxylates catalysts, and other catalyzer comprises metal oxide and metal alkoxide, for example the carboxylate salt of tin, zinc and aluminium, oxide compound and alkoxide.
The NCC-PLA nano-complex that makes thus is the hydrophobicity supramolecular materials, and it can be dispersed in the suitable solvent or drying.For example, it can be used as or further derive the vehicle as drug delivery or release potentially.Adopt the conventional polymer processing technology, such as coextrusion, blowing, injection moulding or compression moulding, it can be further used for mixing with PLA and/or other biological polymer such as poly butyric ester PHB or polyhydroxyalkanoates, with film and/or the three-dimensional mouldable product for the preparation of packing and other industrial application.It can also further be made into emulsion, and melting and electrospinning fibroblast dimension and/or yarn is used for textiles and engineering is used.
Therefore nano-complex of the present invention can be used for multiple industry and medical use, such as but not limited to, packing, automobile, structure, drug release and send, organizational project, be used for support and/or the industrial application of development medical science new system.
NCC-PLA nano-complex of the present invention is supramolecular materials, and it can be suspended in the suitable solvent or dry also being used as potentially or further derivative vehicle as drug delivery and release.
Composition of the present invention comprises nano-complex of the present invention, itself and polymkeric substance be PLA and/or other biological polymer such as poly butyric ester PHB or polyhydroxyalkanoates compounding or blend for example, for example adopt the conventional polymer working method, such as coextrusion, blowing, injection moulding or compression moulding, can be for the preparation of film and/or the three-dimensional mouldable goods of packing and other industrial application.
Said composition can also further be made emulsion, and melting or electrospinning fibroblast dimension and/or yarn is used for textiles and engineering is used.
According to the preparation of NCC-PLA nano-complex of the present invention as described in the step of Fig. 1.Core procedure is the original position ring-opening polymerization of L-rac-Lactide in suitable organic medium in the presence of nanocrystalline Mierocrystalline cellulose (NCC).Before ring-opening polymerization, need through the dispersion medium exchange, if this situation typically, NCC is dispersed in water.After the polymerization, need refined product, for example adopt to the dialysis of water and with methanol wash and, if necessary, washing with acetone.Methyl alcohol is used for removing any unreacted monomer and catalyzer, and acetone is used for the free PLA homopolymer of dissolution system, namely is not grafted to the PLA on the NCC.It below is the detailed description of polymerization technique.
1.NCC typically make the suspension of the variable nanoparticle of concentration in water, 4.39%w/w for example, and be purpose of the present invention, NCC suspension is neutral pH with the titration of NaOH solution.Suspension medium is exchanged into suitable organic solvent from water, dimethyl sulfoxide (DMSO) (DMSO for example, typically＞99.6%), its by for example slowly topple in the aqeous suspension of 30g NCC to the NCC of required quality and stir volume required DMSO for example 110ml carry out.Then mixture is stirred another section reasonable time, for example 5 minutes, so that water and DMSO fully mix.In rotatory evaporator (for example BUCHI, Rotavapor R-200), remove water in the system by the distillation of two steps.In the first step, distillation temperature is elected 83 ℃ as, and vacuum tightness is set to 720 holders.When finishing near the first step, the volume of condensed fluid remains unchanged in the collector.In second step, vacuum tightness increases to 740 and holds in the palm to steam～20ml DMSO.
2. above-mentioned dispersion medium exchange step can replace by freeze-drying or the spray-dired NCC of dispersion (neutral pH) directly are dissolved among the DMSO.Dissolution process can use ultrasonic promotion.Then with container sealing stoping the DMSO absorbing moisture, and stir content, preferably spend the night, if perhaps need then the longer time.
3. in the NCC/DMSO suspension in airtight flask, add as follows: (i) suitable quality 39.5gL-rac-Lactide (typical purity 〉=98%) for example, (ii) the suitable catalyzer of 0.4g, for example 2 ethyl hexanoic acid tin (II) (Sn (oct) 2,～95%), and (iii) 0.2g phenylcarbinol (anhydrous, 99.8%), it is particularly useful for improving the dispersion of NCC in high rac-Lactide consumption situation.Stirring one period reasonable time for example after 5 minutes, suspension was with ultrasonic 2 minutes of probe ultrasonic apparatus (for example Fisher Sonic Dismembrator, Model 300).In the system remaining trace water finally by with suspension by 250ml be filled with the 60g molecular sieve (
Figure BPA00001640528100071
The 8-12 order) separating funnel removes, and described molecular sieve is in advance 320 ℃ of lower activation at least 3 hours.Then dry NCC/DMSO suspension directly splash into the 500ml there-necked flask of the oven dry that mechanical stirrer is housed from funnel.In order to stop the DMSO absorbing moisture, separating funnel and flask all remain under the nitrogen atmosphere in the whole polymerization process.
4. ring-opening polymerization was carried out by airtight flask is soaked in 130 ℃ of oil baths in 17 hours.During reaction, with magnetic force or the mechanical stirrer speed stirred suspension with 200-500rpm.After the reaction, the product that obtains is the transperent suspension liquid of fulvescent.
5. by product, is precipitated out the NCC-PLA nano-complex slowly in the impouring water and rapid stirring with 3: 1 ratio (water/product) from DMSO.Purify subsequently, wherein with flowing water dialysis product at least 4 days (the molecular weight cut-off MWCO=12000-14000 of suggestion) in dialysis tubing for example, and/or with white precipitate with suitable centrifugal system (IEC Centra for example
Figure BPA00001640528100072
MP4, Rotor 224) the centrifugation reasonable time under 4400rpm speed, for example 20 minutes.Behind the decant, product is dispersed in (〉=99.8%) in the methyl alcohol again by shaking to separate with recentrifuge.This centrifugation-decant is cycled to repeat rational number of times, and for example 3 times, with all impurity of flush away.At last, with washed product dry reasonably time under vacuum, for example spend the night.
6. the visual comparison of original NCC and the suspension of NCC-PLA supermolecule nano matrix material in chloroform shows the latter's perfect dispersibility in suitable organic solvent, further shows the hydrophobicity of NCC-PLA nano-complex.
Embodiment 1
The NCC-PLA nano composite material that the in-situ polymerization that utilizes the present invention to describe makes is made particulate, and it has equivalent sphere (being measured by Zetasizer) the typical fluid kinetic diameter that equals 60.2 ± 0.9nm (being scattered in DMSO).Nano composite material is dispersed in the typical organic solvent fully, and this shows fabulous hydrophobicity.The mass ratio of graftomer and NCC typically＞80%.As shown in Figure 2 is solid-state 13C nucleus magnetic resonance (NMR) has confirmed synthetic success.
Embodiment 2
The physics of polymkeric substance or polymer complex, machinery and barrier property depend on solid-state form and the degree of crystallinity of material, and the processing of these matrix materials can affect these performances significantly.NCC-PLA nano composite material of the present invention can utilize the polymer processing technology (such as casting film, extrude/blowing, injection moulding or compression moulding, spin fine etc.) process to produce film, fiber, long filament and general any three-dimensional article.Fig. 3 has described the means of differential scanning calorimetry response of the NCC-PLA nano-complex film that contains 5.3%w/w NCC.These nano-complex films have showed structure and the thermostability of comparing remarkable improvement with pure PLA film, and lower hygroexpansivity.The performance of this uniqueness causes controlled crystallization by NCC and is being undisturbed the ability generation that keeps the NCC structure under the state simultaneously in amorphous PLA.Little and faulty PLA crystal changes more stable crystal in succession by melting and recrystallize (shown in two melting peaks of the NCC-PLA nano-complex of Fig. 3).The dynamic mechanical analysis data acknowledgement that this further presents by Fig. 4, it shows it is how the NCC of compatibilized plays along with the raising of NCC content and improve the PLA softening performance that NCC-PLA prepared in accordance with the present invention plays molecular material thus.There is the increase of an order of magnitude in it aspect the mechanical response of measuring by storage modulus for example, from the 480MPa of 41MPa to the 50 ℃ of lower 5%w/w NCC content of pure PLA.If materials processing becomes rapid cooling (Fig. 5) from Slow cooling (Fig. 4) (wherein degree of crystallinity allows to bring up to the higher order of magnitude), NCC still plays the effect of the degree of crystallinity of improving the composite product that obtains, although speed is lower, because PLA is in this case for fully unbodied.The difference of this improvement amplitude is mainly due to different processing technologies.Used processing technology no matter, two embodiment, Fig. 4 and Fig. 5 clearly illustrate that still NCC improves the effect of the finished product degree of crystallinity.
Owing to being important for the moulded parts thermostability, the degree of crystallinity of raising is expected for moulded parts.In addition, the NCC-PLA nano-complex has showed distinguished visco-elasticity, processing and functionalized aspect have active influence.Processibility, convertibility and mechanical property that the article that comprise the NCC-PLA nano composite material that these performances cause obtaining improve.
The PLA polymkeric substance that nano-complex of the present invention can for example have 20000 to 1000000 weight-average molecular weight with high molecular PLA polymkeric substance is by coextrusion, casting or other conventional blend or the blend of compounding technology or compounding, and the PLA that been significantly enhanced of the existence of nano-complex.
Under this particular case, the molecular weight of grafting PLA is measured by two kinds of indirect methods.(1) carries out control experiment with the same procedure of preparation NCC-PLA nano-complex not having in the NCC situation rac-Lactide to be aggregated into PLA.The polymkeric substance gpc analysis that obtains.(2) second method comprises the free PLA homopolymer of collection from the NCC-PLA preparation process, then with its usefulness 1H NMR characterizes.Ratio according to repeating unit on end group and the main chain calculates molecular weight.Number-average molecular weight in specific embodiment (Mn) scope will be between 890 to 6000 according to polymeric reaction condition, and it is long that this shows that grafting PLA typically has a short chain.By the balanced reaction condition, might allow in theory the PLA chain of growing longer, and prepare thus the grafting PLA of high molecular at NCC.
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Claims (21)

1. prepare the method for sodium rice crystal fiber element (NCC) and poly(lactic acid) (PLA) nano-complex, it is included in the ring-opening polymerization of L-rac-Lactide in the presence of the NCC particle in the non-aqueous media.
2. according to claim 1 method, wherein said ring-opening polymerization is carried out under anhydrous condition.
3. according to claim 1 and 2 method further comprises the step that reclaims described nano-complex from described non-aqueous media.
4. each method according to claim 1-3, wherein said ring-opening polymerization is carried out in organic solvent.
5. according to claim 4 method, wherein said organic solvent is dimethyl sulfoxide (DMSO).
6. according to claim 3 method, wherein said recovery comprises the described nano-complex of precipitation from described non-aqueous media, and the precipitation of purifying and obtaining by dialysis.
7. each method according to claim 1-6, wherein said ring-opening polymerization is being carried out under the temperature that is improving in the presence of the catalyzer.
8. according to claim 7 method, the temperature of wherein said raising is approximately 100 ℃ to approximately 150 ℃.
9. according to claim 8 method, 1 to 20 hour time is carried out in wherein said ring-opening polymerization under the temperature of described raising.
10. according to claim 9 method, the wherein said time is 15 to 20 hours.
11. each method according to claim 1-10, wherein said ring-opening polymerization is carried out in the presence of the initiator that is used for described ring-opening polymerization, and described initiator has alcohol radical.
12. method according to claim 3, at least a portion of the free PLA homopolymer that wherein makes in ring-opening polymerization is retained in the nano-complex of recovery as processing aid.
13. the nano-complex of nanocrystalline Mierocrystalline cellulose (NCC) and poly(lactic acid) (PLA), wherein said PLA is grafted on the described NCC.
14. the nano-complex of claim 13, wherein the NCC nanocrystal of nano-complex has and is connected thereto independently and from several or a plurality of polymer chains of its radiation.
15. according to claim 13 or 14 nano-complex, it has 30% to the PLA percentage of grafting that surpasses 90%.
16. nano-complex according to claim 15, wherein said percentage of grafting are approximately 85%.
17. composition, it comprises each nano-complex of claim 13-16, and its use is extruded, injection moulding or compression moulding and be selected from compounding of polymers or the blend of PLA, poly butyric ester (PHB) or polyhydroxyalkanoate (PHA).
18. composition according to claim 17, wherein said polymkeric substance are high molecular PLA.
19. composition according to claim 18, wherein said PLA has 20,000 to 1,000,000 molecular weight.
20. each composition according to claim 17-19, it is the film that is used for packing and other industrial application or the form of three-dimensional shaped bodies.
21. each composition according to claim 17-19, it is the emulsion, melt-spun or the electrospinning fibre that are used for textiles and engineering and use or the form of yarn.
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